CA2023166A1 - Polyarylene ethers - Google Patents
Polyarylene ethersInfo
- Publication number
- CA2023166A1 CA2023166A1 CA 2023166 CA2023166A CA2023166A1 CA 2023166 A1 CA2023166 A1 CA 2023166A1 CA 2023166 CA2023166 CA 2023166 CA 2023166 A CA2023166 A CA 2023166A CA 2023166 A1 CA2023166 A1 CA 2023166A1
- Authority
- CA
- Canada
- Prior art keywords
- formula
- mol
- group
- structural unit
- recurring structural
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
- 229920000412 polyarylene Polymers 0.000 title claims abstract description 25
- 150000002170 ethers Chemical class 0.000 title abstract description 16
- 229920005989 resin Polymers 0.000 claims abstract description 7
- 239000011347 resin Substances 0.000 claims abstract description 7
- 229920000570 polyether Polymers 0.000 claims abstract description 6
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 20
- 150000001875 compounds Chemical class 0.000 claims description 10
- PPTXVXKCQZKFBN-UHFFFAOYSA-N (S)-(-)-1,1'-Bi-2-naphthol Chemical compound C1=CC=C2C(C3=C4C=CC=CC4=CC=C3O)=C(O)C=CC2=C1 PPTXVXKCQZKFBN-UHFFFAOYSA-N 0.000 claims description 9
- -1 alkali metal phenolate Chemical class 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 5
- XKZQKPRCPNGNFR-UHFFFAOYSA-N 2-(3-hydroxyphenyl)phenol Chemical compound OC1=CC=CC(C=2C(=CC=CC=2)O)=C1 XKZQKPRCPNGNFR-UHFFFAOYSA-N 0.000 claims description 4
- 229940031826 phenolate Drugs 0.000 claims description 4
- 229910052783 alkali metal Inorganic materials 0.000 claims description 3
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 3
- 239000003054 catalyst Substances 0.000 claims description 3
- 238000006068 polycondensation reaction Methods 0.000 claims description 3
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 2
- 125000001153 fluoro group Chemical group F* 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims description 2
- 239000003880 polar aprotic solvent Substances 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 claims description 2
- 239000012770 industrial material Substances 0.000 abstract description 5
- 229920000642 polymer Polymers 0.000 description 6
- LSQARZALBDFYQZ-UHFFFAOYSA-N 4,4'-difluorobenzophenone Chemical compound C1=CC(F)=CC=C1C(=O)C1=CC=C(F)C=C1 LSQARZALBDFYQZ-UHFFFAOYSA-N 0.000 description 4
- KZTYYGOKRVBIMI-UHFFFAOYSA-N diphenyl sulfone Chemical compound C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 description 4
- 229920001643 poly(ether ketone) Polymers 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 230000003014 reinforcing effect Effects 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 239000008096 xylene Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 229950011260 betanaphthol Drugs 0.000 description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- AVQQQNCBBIEMEU-UHFFFAOYSA-N 1,1,3,3-tetramethylurea Chemical compound CN(C)C(=O)N(C)C AVQQQNCBBIEMEU-UHFFFAOYSA-N 0.000 description 1
- PLVUIVUKKJTSDM-UHFFFAOYSA-N 1-fluoro-4-(4-fluorophenyl)sulfonylbenzene Chemical compound C1=CC(F)=CC=C1S(=O)(=O)C1=CC=C(F)C=C1 PLVUIVUKKJTSDM-UHFFFAOYSA-N 0.000 description 1
- RXNYJUSEXLAVNQ-UHFFFAOYSA-N 4,4'-Dihydroxybenzophenone Chemical compound C1=CC(O)=CC=C1C(=O)C1=CC=C(O)C=C1 RXNYJUSEXLAVNQ-UHFFFAOYSA-N 0.000 description 1
- OKISUZLXOYGIFP-UHFFFAOYSA-N 4,4'-dichlorobenzophenone Chemical compound C1=CC(Cl)=CC=C1C(=O)C1=CC=C(Cl)C=C1 OKISUZLXOYGIFP-UHFFFAOYSA-N 0.000 description 1
- GPAPPPVRLPGFEQ-UHFFFAOYSA-N 4,4'-dichlorodiphenyl sulfone Chemical compound C1=CC(Cl)=CC=C1S(=O)(=O)C1=CC=C(Cl)C=C1 GPAPPPVRLPGFEQ-UHFFFAOYSA-N 0.000 description 1
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 1
- NZGQHKSLKRFZFL-UHFFFAOYSA-N 4-(4-hydroxyphenoxy)phenol Chemical compound C1=CC(O)=CC=C1OC1=CC=C(O)C=C1 NZGQHKSLKRFZFL-UHFFFAOYSA-N 0.000 description 1
- 241000531908 Aramides Species 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- ZWXPDGCFMMFNRW-UHFFFAOYSA-N N-methylcaprolactam Chemical compound CN1CCCCCC1=O ZWXPDGCFMMFNRW-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- PISLKPDKKIDMQT-UHFFFAOYSA-N [3-(4-fluorobenzoyl)phenyl]-(4-fluorophenyl)methanone Chemical compound C1=CC(F)=CC=C1C(=O)C1=CC=CC(C(=O)C=2C=CC(F)=CC=2)=C1 PISLKPDKKIDMQT-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000000010 aprotic solvent Substances 0.000 description 1
- 229920003235 aromatic polyamide Polymers 0.000 description 1
- 239000010425 asbestos Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- VCCBEIPGXKNHFW-UHFFFAOYSA-N biphenyl-4,4'-diol Chemical group C1=CC(O)=CC=C1C1=CC=C(O)C=C1 VCCBEIPGXKNHFW-UHFFFAOYSA-N 0.000 description 1
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- ZMRQTIAUOLVKOX-UHFFFAOYSA-L calcium;diphenoxide Chemical class [Ca+2].[O-]C1=CC=CC=C1.[O-]C1=CC=CC=C1 ZMRQTIAUOLVKOX-UHFFFAOYSA-L 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 125000004218 chloromethyl group Chemical group [H]C([H])(Cl)* 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000002050 diffraction method Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- AJFDBNQQDYLMJN-UHFFFAOYSA-N n,n-diethylacetamide Chemical compound CCN(CC)C(C)=O AJFDBNQQDYLMJN-UHFFFAOYSA-N 0.000 description 1
- NXPPAOGUKPJVDI-UHFFFAOYSA-N naphthalene-1,2-diol Chemical compound C1=CC=CC2=C(O)C(O)=CC=C21 NXPPAOGUKPJVDI-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 229910052895 riebeckite Inorganic materials 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
- C08G65/38—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols
- C08G65/40—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols from phenols (I) and other compounds (II), e.g. OH-Ar-OH + X-Ar-X, where X is halogen atom, i.e. leaving group
- C08G65/4012—Other compound (II) containing a ketone group, e.g. X-Ar-C(=O)-Ar-X for polyetherketones
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
- C08G75/20—Polysulfones
- C08G75/23—Polyethersulfones
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyethers (AREA)
Abstract
K- 17697/+ /CGM349 Novel polyarylene ethers Abstract Polyarylene ethers which contain, based on the total amount of structural units present in the polyether resin, 10-100 mol % of a recurring structural unit of the formula I
(I), 0-50 mol % of a recurring structural unit of the formula II
(II), 0-90 mol % of a recurring structural unit of the formula III
?O-A"-O-A] (III), and 0-50 mol % of a recurring structural unit of the formula IV
?O-A"-C)-A'] - (IV), in which A is a group of the formula Va or Vb (Va) (Vb) in which X is -CO-, a is 0, 1 or 2 and b is 2 or 3, and A' is a group of the formula VIa or VIb (VIa) (VIb) in which Y is -SO- or -SO2-, c is 0 or 1 and d is 2, and A" is a group of the formulae VIIa to VIIe (VIIa), (VIIb), (VIIc), (VIId) or (VIIe), in which Z is a direct bond, -C(CH3)2-, -C(CF3)2-, -S-, SO-, -SO2-, -O- or -CO-.
These industrial materials have very good mechanical and thermal properties.
(I), 0-50 mol % of a recurring structural unit of the formula II
(II), 0-90 mol % of a recurring structural unit of the formula III
?O-A"-O-A] (III), and 0-50 mol % of a recurring structural unit of the formula IV
?O-A"-C)-A'] - (IV), in which A is a group of the formula Va or Vb (Va) (Vb) in which X is -CO-, a is 0, 1 or 2 and b is 2 or 3, and A' is a group of the formula VIa or VIb (VIa) (VIb) in which Y is -SO- or -SO2-, c is 0 or 1 and d is 2, and A" is a group of the formulae VIIa to VIIe (VIIa), (VIIb), (VIIc), (VIId) or (VIIe), in which Z is a direct bond, -C(CH3)2-, -C(CF3)2-, -S-, SO-, -SO2-, -O- or -CO-.
These industrial materials have very good mechanical and thermal properties.
Description
2 ~ 2 3 ~ ~ ~
K-17697/+/CGM 349 Novel polvarvlene ethers The present invention relates to novel polyarylene ethers, to a process for their preparation and to their use as industrial materials.
EP-A-282,096 describes the synthesis of polyarylene ether ketones and sulfones containing l,l'-bis-4-naphthoxy structural units. Aliphatic-aromatic polyethers of diphenols and bis(chloromethyl) derivatives containing units of the 2,2'-dihydroxy-1,1'-dinaphthyl type are furthermore known from M. Tokarzewska, J. Pol.
Sci., Part A-l, Volume 6,777-784, (1968). Polyether ketones containing structural units which are derived from napthalenediols are also described in Japanese Patent Kokai 213,219/86; 11,726/87 and 7~,032/88.
These polymers do not meet in every respect the stringent demands made toclay of a high quality thermoplastic resin. In particular, the glass transition point is unsatisfactoIy, leading to inadequate dimensional stability under heat or to generally inadequate heat stability. The resistance to solvents is furtherrnore insufficient.
The object of the present invention is to provide polyaIylene ethers which are suitable industrial materials having very good mechanical properties and at the same time have a low melting point, a high glass transition temperature, good resistance to solvents and, preferably, partial crystallinity.
Surprisingly, this object is achieved by incorporating structural units which are derived from 2,2'-dihydroxydinaphthyl into the polyarylene ether ketone chain.
The present invention relates to polyarylene ethers which contain, based on the total amount of structural units present in the polyether resin, 10- 100 mol % of a recurring structural unit of the forrnula I
,. . .. .
. . .
~~ 1 (1), ~ ~0--At 0-50 mol % of a recurring structural unit of the forrnula II
~o~3 ~ (l:I), ~ ~0--A~
0-90 mol % of a recurring structural unit of the forrnula III
~0--A"--O--kl-- (III) and 0-50 mol % of a recurring structural unit of the formula IV
~0--A"--O--A' ] (IV), in which A is a group of the formula Va or Vb ~x ~i3X ~ (Va) ~3x ~X~3 (Vb) in which X is -CO-, a is 0, 1 or 2 and b is 2 or 3~ and A' is a group of the formula VIa or VIb ~ Y ~3 y ~ (VIa) :
:, - , , . ~
, ~ , . ~
- : . ~
., , '' ~, ; ':
.
2~
~Y ~ Y~3 (VIb) in which Y is -SO- or -SO2-, c is O or 1 and d is 2, and A" is a group of the formulae VIIa to VIIe ~3 (VIIa), ~ (VIIb3, ~3 Z ~} (VIIC), ~3z ~ Z ~ (VIId) or ~3 z ~3 z ~ z ~} (VIIe)~
in which Z is a direct bond, -C(CH3)2-, -C(CF3)2-, -S-, -SO-, -SO2-, -O- or -CO-.
The polyarylene ethers according to the invention preferably contain 25-100 mol % of a recurring structural unit of the ~ormula I and 0-75 mol % of a recurring structural unit of the formula III and/or 0-50 mol % of a recurring structural unit of the formula IV.
Particularly preferred polyarylene ethers are those in which A is a group of the formula Va, in particular in which a has the value zero.
Polyarylene ethers in which A' is a group of the formula VIa, in particular in which c is zero, are likewise preferred.
The preferred meaning of Y in the formulae VIa and VIb is -SO2-.
Polyarylene ethers in which A" is a group of the forrnulae VIIa and/or VIIc, in which Z is -CO- or a direct bond, are specifically preferred.
Polyarylene ethers in which A in the formulae I and/or III is the group ~ c ~ and A' in the formulae [I and IV is the group ., , ., . -. ~ ~
. .:. . . .
:
~ so2~ are of very particular interest.
The polyarylene ethers according to the invention can be prepared, for example, by subjecting a compound of the formulae VIIIa, VIIIb, lXa and/or IXb Hal ~C~x )~Hal ~VIIIa) Hal ~X ~--~X ~Hal (VIIIb~
Hal ~ Y ~3 Y ~3 Hal (IXa) Hal ~3Y~Y~Hal (lXb~
in which X, Y, a, b, c and d are as defined above and Hal is halogen, in particular fluoro or chloro, to a polycondensation reaction with l,l'-bis-2-naphthol by itself or with a mixture of this compound and a diphenol which is present therein in an amout of up to 90 mol %, of the formula X
HO-A"-OH (X) in which A" is as defined above, in a manner which is known per se, in the presence of alkaline catalysts in a polar aprotic solvent.
Instead of the diphenol of the formula X or the 1,1'-bis-2-naphthol, the corresponding alkali metal phenolate or alkaline earth metal phenolate, for example the potassium or calcium phenolates or corresponding mixtures, can also be employed in a manner which is known per se.
The polycondensation reaction is usually carried out in approximately equimolar ratios of , .:
the compounds VIIIa, VIlIb, l~a, ~b:l,1'-bis-2-naphthol or (1,1'-bis-2-naphthol + X).
Approximately equimolar amounts is understood in this connection as meaning a molar ratio of 0.8:1.2 to 1.2:0.8. A rnolar ratio of 0.95:1.05 to 1.05:0.95 is preferred.
Alkaline catalysts which are used in this process are as a rule alkali metal carhona~es and alkaline earth metal carbonates, such as sodium carbonate, potassium carbonate or calcium carbonate, or mixtures thereof, however, other alkaline reagents, such as sodium hydroxide, potassium hydroxide or calcium hydroxide, can also be used.
Examples of polar, aprotic solvents which can be employed in the process for thepreparation of the polyether resins according to the invention are dimethyl sulfoxide, dimethylacetamide, diethylacetamide, tetramethylurea, N-methylcaprolactam, N-methylpyrrolidone and preferably diphenyl sulfone.
The reaction is advantageously carried out at elevated temperatures, preferably up to the reflux temperature of the solvent, that is to say for example up to 350C.
It is often advisable also to use an entraining agent, for example chlorobenzene, xylene or toluene, so that the water formed during the reaction can be removed azeotropically from the reaction mixture.
The compounds of the formulae VIIIa, VIIIb, IXa and IXb are known and are in some cases commercially available. Examples of suitable compounds of these formulae are 4,4'-difluorobenzophenone, 1,3-bis(4-fluorobenzoyl)benzene, 4,4'-dichlorobenzophenone, 4,4'-difluorodiphenyl sulfone or 4,4'-dichlorodiphenyl sulfone.
1,1 '-bis-2-naphthol is known and is commercially available.
The compounds of the formula X are also known compounds and are in rnost cases commercially available. Examples of sui~able dihydric phenols of the forrnula VI are hydroquinone, resorcinol, 4,4'-dihydroxydiphenyl, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxydiphenyl sulfone, 4,4'-dihydroxybenzophenone, 4,4'-dihydroxydiphenylmethane, 4,4'-dihydroxydiphenyl thioether, 2,2-di-(4-hydroxyphenyl)propane and dihydroxynaphthalene.
The polyether resins according to the invention can be employed in the conventional .
7J ~
manner for therrnoplastics and can be processed, for example, to mouldings o} sheets or they can be used as matrix resins, adhesives or coating compounds. The customaryadditives, for example, fillers, pigments, stabilizers or reinforcing agents, such as carbon fibres, boron ~Ibres or glass fibres, can be added before processing of the polyarylene ether which is for example, in the form of a moulding powder, film or melt. Another possible use of the polyarylene ethers according to the invention is the modification of other plastics. These can in principle be thermoplastics or thermosets.
The polyarylene ethers according to the invention are preferably suitable as matrix resins for the production of fibre composite systems, for which utility it is possible to use as reinforcing fibres the fibres conventionally used for reinforcing industrial materials. These fibres can be organic or inorganic ~Ibres, naturally occurring fibres or synthetic fibres, such as aramide fibres, and can be in the form of fibre bundles, oriented or non-oriented ~Ibres or continuous fibres. Glass ~Ibres, asbestos fibres, boron ~Ibres, carbon fibres and metal fibres, for example, are used as the reinforcing fibres.
As the range of utility described above shows, the polyarylene ethers of this invention are widely applicable as industrial materials.
Examples 1-~: A mixture of 28.63 g (0.1000 mol) of 1,1'-bis-2-naphthol,75.68 g of diphenyl sulfone, 15.53 g (0.1124 mol) of potassium carbonate and 57.6 g of xylene is heated at a bath temperature of 200C under nitrogen in a round-bottomed flask with a stirrer, inert gas connection and distillation unit, and a xylene/water mixture is distilled off. Towards the end of the distillation, vacuum (5 mbar) is applied for a short time. 21.40 g (0.0981 mol) of 4,4'-difluorobenzophenone are then added to the reaction rnixture and the temperature is increased to 250C at 2(:/minute and kept for 1 hour. The temperature is subsequently further increased to 320C. Rfter 1.5 hours, 0.49 g (0.0023 mol) of 4,4'-difluorobenzophenone is added, and after a futher 30 minutes another 0.24 g (0.0011 mol) of 4,4'-difluorobenzophenone is added. The temperature is then increased to 350C
and kept for 3.5 hours.
After cooling, the reaction mixture is removed from the flask and pulverised. 2 molar hydrochloric acid is added and the mixture is extracted first with water and then with acetone. The polymer purified in this way is dried in a vacuum drying cabinet at a temperature of up to 240C. A polyether ketone prepared in this manner and containing bisnaphthol units has a glass aansition temperature, determined by DSC, of 225C and a s33 ~
melting point of 310C.
Examples 2-6 shown in the following table are prepared in similar manner.
The polymers are insoluble in acectone and methylene chloride and only sparingly soluble (< 1 %) in N-methylpyrrolidone, but are soluble in concentrated sulfuric acid to give a gel-free solution. The solubility in concentrated sulfuric acid demonstrates the presence of a linear, i.e. non-crosslinked, polyether ketone.
X-ray analysis shows that the polymers contain distinct crystalline fractions. The relative crystallinity of selected examples is deterrnined by radiographic analysis by means of powder diffractometry (Philips PW 1710 powder dfflractometer) with CuKa-irradiation in reflection geometry. The values reported in Table 2 (ra~io of crystalline surface to crystalline and amorphous surface = degree of crystallinity; evaluation in accordance with C.-L. Ong, W.-L. Chung, M.-F. Sheu, J.-H. Lin 33rd Int. SAMPE Symposium 1988, p.1307) indicate clearly that (partially) crystalline polymers are obtained.
A polyether ketone prepared according to Example 2 is pressed in a plate press at 250C
under a force of 3000 N for 10 minutes. A flexible film which can be bent and folded repeatedly without fracture is obtained. The film (thickness: 0.13 mm) has a tensile strength of 60 MPa and an elongation at break of 8 % (according to DIN 53 455).
':
. , ,:
. .
' 7 -~ -~ o o~ ~
o ~ ~ ~o~ ~
- - : -~ ~ 1~' ''' oo o ç~
~` 2 . ; . . . . ~ ... ~,.. .. .
;
.
" . ..
~3~ ~
E 1:1 . .
~ ~ I
o~ _ ~ _ __ :'Y o o CC CJv, C~ go ~
~ O O ~ ~ _. O O ~ C`l !
Table 2: Relative Crystallinity vf the polymers synthesised with 1,1'-bis-2-naphthol . ._ _ Example of Table 1 Degree of crystallinity . _ 1 not determined 2 0.24 3 0.46 4 0.47 0.35 6 0.39 7 not detennined 8 0.17 9 0.37 _ _ _ _ _ :
. .
K-17697/+/CGM 349 Novel polvarvlene ethers The present invention relates to novel polyarylene ethers, to a process for their preparation and to their use as industrial materials.
EP-A-282,096 describes the synthesis of polyarylene ether ketones and sulfones containing l,l'-bis-4-naphthoxy structural units. Aliphatic-aromatic polyethers of diphenols and bis(chloromethyl) derivatives containing units of the 2,2'-dihydroxy-1,1'-dinaphthyl type are furthermore known from M. Tokarzewska, J. Pol.
Sci., Part A-l, Volume 6,777-784, (1968). Polyether ketones containing structural units which are derived from napthalenediols are also described in Japanese Patent Kokai 213,219/86; 11,726/87 and 7~,032/88.
These polymers do not meet in every respect the stringent demands made toclay of a high quality thermoplastic resin. In particular, the glass transition point is unsatisfactoIy, leading to inadequate dimensional stability under heat or to generally inadequate heat stability. The resistance to solvents is furtherrnore insufficient.
The object of the present invention is to provide polyaIylene ethers which are suitable industrial materials having very good mechanical properties and at the same time have a low melting point, a high glass transition temperature, good resistance to solvents and, preferably, partial crystallinity.
Surprisingly, this object is achieved by incorporating structural units which are derived from 2,2'-dihydroxydinaphthyl into the polyarylene ether ketone chain.
The present invention relates to polyarylene ethers which contain, based on the total amount of structural units present in the polyether resin, 10- 100 mol % of a recurring structural unit of the forrnula I
,. . .. .
. . .
~~ 1 (1), ~ ~0--At 0-50 mol % of a recurring structural unit of the forrnula II
~o~3 ~ (l:I), ~ ~0--A~
0-90 mol % of a recurring structural unit of the forrnula III
~0--A"--O--kl-- (III) and 0-50 mol % of a recurring structural unit of the formula IV
~0--A"--O--A' ] (IV), in which A is a group of the formula Va or Vb ~x ~i3X ~ (Va) ~3x ~X~3 (Vb) in which X is -CO-, a is 0, 1 or 2 and b is 2 or 3~ and A' is a group of the formula VIa or VIb ~ Y ~3 y ~ (VIa) :
:, - , , . ~
, ~ , . ~
- : . ~
., , '' ~, ; ':
.
2~
~Y ~ Y~3 (VIb) in which Y is -SO- or -SO2-, c is O or 1 and d is 2, and A" is a group of the formulae VIIa to VIIe ~3 (VIIa), ~ (VIIb3, ~3 Z ~} (VIIC), ~3z ~ Z ~ (VIId) or ~3 z ~3 z ~ z ~} (VIIe)~
in which Z is a direct bond, -C(CH3)2-, -C(CF3)2-, -S-, -SO-, -SO2-, -O- or -CO-.
The polyarylene ethers according to the invention preferably contain 25-100 mol % of a recurring structural unit of the ~ormula I and 0-75 mol % of a recurring structural unit of the formula III and/or 0-50 mol % of a recurring structural unit of the formula IV.
Particularly preferred polyarylene ethers are those in which A is a group of the formula Va, in particular in which a has the value zero.
Polyarylene ethers in which A' is a group of the formula VIa, in particular in which c is zero, are likewise preferred.
The preferred meaning of Y in the formulae VIa and VIb is -SO2-.
Polyarylene ethers in which A" is a group of the forrnulae VIIa and/or VIIc, in which Z is -CO- or a direct bond, are specifically preferred.
Polyarylene ethers in which A in the formulae I and/or III is the group ~ c ~ and A' in the formulae [I and IV is the group ., , ., . -. ~ ~
. .:. . . .
:
~ so2~ are of very particular interest.
The polyarylene ethers according to the invention can be prepared, for example, by subjecting a compound of the formulae VIIIa, VIIIb, lXa and/or IXb Hal ~C~x )~Hal ~VIIIa) Hal ~X ~--~X ~Hal (VIIIb~
Hal ~ Y ~3 Y ~3 Hal (IXa) Hal ~3Y~Y~Hal (lXb~
in which X, Y, a, b, c and d are as defined above and Hal is halogen, in particular fluoro or chloro, to a polycondensation reaction with l,l'-bis-2-naphthol by itself or with a mixture of this compound and a diphenol which is present therein in an amout of up to 90 mol %, of the formula X
HO-A"-OH (X) in which A" is as defined above, in a manner which is known per se, in the presence of alkaline catalysts in a polar aprotic solvent.
Instead of the diphenol of the formula X or the 1,1'-bis-2-naphthol, the corresponding alkali metal phenolate or alkaline earth metal phenolate, for example the potassium or calcium phenolates or corresponding mixtures, can also be employed in a manner which is known per se.
The polycondensation reaction is usually carried out in approximately equimolar ratios of , .:
the compounds VIIIa, VIlIb, l~a, ~b:l,1'-bis-2-naphthol or (1,1'-bis-2-naphthol + X).
Approximately equimolar amounts is understood in this connection as meaning a molar ratio of 0.8:1.2 to 1.2:0.8. A rnolar ratio of 0.95:1.05 to 1.05:0.95 is preferred.
Alkaline catalysts which are used in this process are as a rule alkali metal carhona~es and alkaline earth metal carbonates, such as sodium carbonate, potassium carbonate or calcium carbonate, or mixtures thereof, however, other alkaline reagents, such as sodium hydroxide, potassium hydroxide or calcium hydroxide, can also be used.
Examples of polar, aprotic solvents which can be employed in the process for thepreparation of the polyether resins according to the invention are dimethyl sulfoxide, dimethylacetamide, diethylacetamide, tetramethylurea, N-methylcaprolactam, N-methylpyrrolidone and preferably diphenyl sulfone.
The reaction is advantageously carried out at elevated temperatures, preferably up to the reflux temperature of the solvent, that is to say for example up to 350C.
It is often advisable also to use an entraining agent, for example chlorobenzene, xylene or toluene, so that the water formed during the reaction can be removed azeotropically from the reaction mixture.
The compounds of the formulae VIIIa, VIIIb, IXa and IXb are known and are in some cases commercially available. Examples of suitable compounds of these formulae are 4,4'-difluorobenzophenone, 1,3-bis(4-fluorobenzoyl)benzene, 4,4'-dichlorobenzophenone, 4,4'-difluorodiphenyl sulfone or 4,4'-dichlorodiphenyl sulfone.
1,1 '-bis-2-naphthol is known and is commercially available.
The compounds of the formula X are also known compounds and are in rnost cases commercially available. Examples of sui~able dihydric phenols of the forrnula VI are hydroquinone, resorcinol, 4,4'-dihydroxydiphenyl, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxydiphenyl sulfone, 4,4'-dihydroxybenzophenone, 4,4'-dihydroxydiphenylmethane, 4,4'-dihydroxydiphenyl thioether, 2,2-di-(4-hydroxyphenyl)propane and dihydroxynaphthalene.
The polyether resins according to the invention can be employed in the conventional .
7J ~
manner for therrnoplastics and can be processed, for example, to mouldings o} sheets or they can be used as matrix resins, adhesives or coating compounds. The customaryadditives, for example, fillers, pigments, stabilizers or reinforcing agents, such as carbon fibres, boron ~Ibres or glass fibres, can be added before processing of the polyarylene ether which is for example, in the form of a moulding powder, film or melt. Another possible use of the polyarylene ethers according to the invention is the modification of other plastics. These can in principle be thermoplastics or thermosets.
The polyarylene ethers according to the invention are preferably suitable as matrix resins for the production of fibre composite systems, for which utility it is possible to use as reinforcing fibres the fibres conventionally used for reinforcing industrial materials. These fibres can be organic or inorganic ~Ibres, naturally occurring fibres or synthetic fibres, such as aramide fibres, and can be in the form of fibre bundles, oriented or non-oriented ~Ibres or continuous fibres. Glass ~Ibres, asbestos fibres, boron ~Ibres, carbon fibres and metal fibres, for example, are used as the reinforcing fibres.
As the range of utility described above shows, the polyarylene ethers of this invention are widely applicable as industrial materials.
Examples 1-~: A mixture of 28.63 g (0.1000 mol) of 1,1'-bis-2-naphthol,75.68 g of diphenyl sulfone, 15.53 g (0.1124 mol) of potassium carbonate and 57.6 g of xylene is heated at a bath temperature of 200C under nitrogen in a round-bottomed flask with a stirrer, inert gas connection and distillation unit, and a xylene/water mixture is distilled off. Towards the end of the distillation, vacuum (5 mbar) is applied for a short time. 21.40 g (0.0981 mol) of 4,4'-difluorobenzophenone are then added to the reaction rnixture and the temperature is increased to 250C at 2(:/minute and kept for 1 hour. The temperature is subsequently further increased to 320C. Rfter 1.5 hours, 0.49 g (0.0023 mol) of 4,4'-difluorobenzophenone is added, and after a futher 30 minutes another 0.24 g (0.0011 mol) of 4,4'-difluorobenzophenone is added. The temperature is then increased to 350C
and kept for 3.5 hours.
After cooling, the reaction mixture is removed from the flask and pulverised. 2 molar hydrochloric acid is added and the mixture is extracted first with water and then with acetone. The polymer purified in this way is dried in a vacuum drying cabinet at a temperature of up to 240C. A polyether ketone prepared in this manner and containing bisnaphthol units has a glass aansition temperature, determined by DSC, of 225C and a s33 ~
melting point of 310C.
Examples 2-6 shown in the following table are prepared in similar manner.
The polymers are insoluble in acectone and methylene chloride and only sparingly soluble (< 1 %) in N-methylpyrrolidone, but are soluble in concentrated sulfuric acid to give a gel-free solution. The solubility in concentrated sulfuric acid demonstrates the presence of a linear, i.e. non-crosslinked, polyether ketone.
X-ray analysis shows that the polymers contain distinct crystalline fractions. The relative crystallinity of selected examples is deterrnined by radiographic analysis by means of powder diffractometry (Philips PW 1710 powder dfflractometer) with CuKa-irradiation in reflection geometry. The values reported in Table 2 (ra~io of crystalline surface to crystalline and amorphous surface = degree of crystallinity; evaluation in accordance with C.-L. Ong, W.-L. Chung, M.-F. Sheu, J.-H. Lin 33rd Int. SAMPE Symposium 1988, p.1307) indicate clearly that (partially) crystalline polymers are obtained.
A polyether ketone prepared according to Example 2 is pressed in a plate press at 250C
under a force of 3000 N for 10 minutes. A flexible film which can be bent and folded repeatedly without fracture is obtained. The film (thickness: 0.13 mm) has a tensile strength of 60 MPa and an elongation at break of 8 % (according to DIN 53 455).
':
. , ,:
. .
' 7 -~ -~ o o~ ~
o ~ ~ ~o~ ~
- - : -~ ~ 1~' ''' oo o ç~
~` 2 . ; . . . . ~ ... ~,.. .. .
;
.
" . ..
~3~ ~
E 1:1 . .
~ ~ I
o~ _ ~ _ __ :'Y o o CC CJv, C~ go ~
~ O O ~ ~ _. O O ~ C`l !
Table 2: Relative Crystallinity vf the polymers synthesised with 1,1'-bis-2-naphthol . ._ _ Example of Table 1 Degree of crystallinity . _ 1 not determined 2 0.24 3 0.46 4 0.47 0.35 6 0.39 7 not detennined 8 0.17 9 0.37 _ _ _ _ _ :
. .
Claims (9)
1. A polyarylene ether which contains, based on the total amount of structural units present in the polyether resin, 10-100 mol % of a recurring structural unit of the formula I
(I), 0-50 mol % of a recurring structural unit of the formula II
(II), 0-90 mol % of a recurring structural unit of the formula III
? O-A"-O-A? (III) and 0-50 mol % of a recurring structural unit of the formula IV
? O-A"-O-A'? (IV), in which A is a group of the formula Va or Vb (Va) (Vb) in which X is -CO-, a is 0, 1 or 2 and b is 2 or 3, and A' is a group of the formula VIa or VIb (VIa) (VIb) in which Y is -SO- or -SO2-, c is 0 or 1 and d is 2, and A" is a group of the formulae VIIa to VIIe (VIIa), (VIIb), (VIIc), (VIId) or (VIIe), in which Z is a direct bond, -C(CH3)2-, -C(CF3)2-, -S-, -SO-, -SO2-, -O- or -CO-.
(I), 0-50 mol % of a recurring structural unit of the formula II
(II), 0-90 mol % of a recurring structural unit of the formula III
? O-A"-O-A? (III) and 0-50 mol % of a recurring structural unit of the formula IV
? O-A"-O-A'? (IV), in which A is a group of the formula Va or Vb (Va) (Vb) in which X is -CO-, a is 0, 1 or 2 and b is 2 or 3, and A' is a group of the formula VIa or VIb (VIa) (VIb) in which Y is -SO- or -SO2-, c is 0 or 1 and d is 2, and A" is a group of the formulae VIIa to VIIe (VIIa), (VIIb), (VIIc), (VIId) or (VIIe), in which Z is a direct bond, -C(CH3)2-, -C(CF3)2-, -S-, -SO-, -SO2-, -O- or -CO-.
2. A polyarylene ether according to claim 1, which contains 25-100 mol % of a recurring structural unit of the formula I and 0-75 mol % of a recurring structural unit of the formula III and/or 0-50 mol % of a recurring structural unit of the formula IV.
3. A polyarylene ether according to claim 1, in which A is a group of the formula Va.
4. A polyarylene ether according to claim 1, in which A' is a group of the formula VIa.
5. A polyarylene ether according to claim 4, in which Y is -SO2-.
6. A polyarylene ether according to claim 1, in which A" in the formulae III and/or IV is a group of the formulae VIIa andlor VIlc, in which Z is -CO- or a direct bond.
7. A polyarylene ether according to claim 1, in which A is the group and A' is the group .
8. A process for a preparation of a polyarylene ether according to claim 1, which comprises subjecting a compound of the folmulae VIIIa, VIIlb, IXa and/or IXb (VIIIa) (VIIIb) (IXa) (IXb) in which X, Y, a, b, c and d are as defined above and Hal is halogen, in particular fluoro or chloro, to a polycondensation reaction with 1,1'-bis-2-naphthol by itself or with a mixture of said compound and a diphenol which is present therein in an amout of up to 90 mol %, of the formula X
HO-A"-OH (X) in which A" is as defined above, in a manner which is known per se, in the presence of alkaline catalysts in a polar aprotic solvent.
HO-A"-OH (X) in which A" is as defined above, in a manner which is known per se, in the presence of alkaline catalysts in a polar aprotic solvent.
9. A process according to clairn 8, wherein the corresponding alkali metal phenolate or alkaline earth metal phenolate is employed instead of the diphenol of the formula X or the 1, 1'-bis-2-naphthol.
FO 7.3/MJ/cc*
FO 7.3/MJ/cc*
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH2974/89-0 | 1989-08-15 | ||
| CH297489 | 1989-08-15 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2023166A1 true CA2023166A1 (en) | 1991-02-16 |
Family
ID=4245821
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA 2023166 Abandoned CA2023166A1 (en) | 1989-08-15 | 1990-08-13 | Polyarylene ethers |
Country Status (3)
| Country | Link |
|---|---|
| EP (1) | EP0413662A3 (en) |
| JP (1) | JPH0388829A (en) |
| CA (1) | CA2023166A1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7176278B2 (en) | 2001-08-30 | 2007-02-13 | Biorexis Technology, Inc. | Modified transferrin fusion proteins |
| CN101511868B (en) | 2006-07-24 | 2013-03-06 | 比奥雷克西斯制药公司 | Exendin fusion proteins |
| GB0625487D0 (en) * | 2006-12-21 | 2007-01-31 | Victrex Mfg Ltd | Composite material |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4806617A (en) * | 1987-03-13 | 1989-02-21 | The B.F. Goodrich Company | Poly(dinaphthyl arylene ether) and preparation thereof |
-
1990
- 1990-08-07 EP EP19900810597 patent/EP0413662A3/en not_active Withdrawn
- 1990-08-13 CA CA 2023166 patent/CA2023166A1/en not_active Abandoned
- 1990-08-15 JP JP21567590A patent/JPH0388829A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| EP0413662A3 (en) | 1991-10-23 |
| EP0413662A2 (en) | 1991-02-20 |
| JPH0388829A (en) | 1991-04-15 |
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